Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
  • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
  • C07C15/50—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals polycyclic non-condensed
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
  • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
  • C07C2527/055—Sulfates or other compounds comprising the anion (SnO3n+1)2- with alkali metals, copper, gold or silver

Definitions

• This invention relates to a substituted styrene polymer having a plurality of pendant vinylidene groups and also to a graft copolymer derived from said substituted styrene polymer.
• the viscosity of a polymer substance is a function of its molecular weight. It is also well-known that branched polymers having star- or comb-like configuration gcnerally have a viscosity lower than straight chain linear polymers having corresponding molecular weights.
• a method for producing a graft copolymer comprising the steps of metallizing poly­(p-methylstyrene)(PPMS) or styrene/p-methylstyrene/sty­rene ternary block copolymer (SMS) with n-butyl lithium/­tetramethylethylenediamine, reacting the resulting pseudogels (precipitates) of metallized polymer with a vinylidene monomer such as 1,1-diphenylethylene (DPE) to form an adduct, and graft-polymerizing acrylic monomers using said adduct as an initiator.
• This method is advantageous in that the adduct is soluble in conventional inert organic solvents and that undesirable side reactions such as carbonyl addition to the metal­lized reaction site do not occur.
• the resulting product often contains a significant amount of homopoly­mers of said acrylic monomers. This is because the starting PPMS or SMS is not fully metallized and thus remaining unreacted metallizing agent serves as an initiator of the homopolymerization of acrylic monomers. This side reaction may be avoided by thoroughly washing the metallized polymer with an organic solvent before reacting with the vinylidene monomer to remove unreacted metallizing agent.
• a graft copolymer by the anion polymerization technique it would be desirable for the synthesis of a graft copolymer by the anion polymerization technique to have a metallized polymer initiator which is soluble in a variety of innert organic solvents and which has a high metallizing efficiency (preferably as nearly as 100%) and a high initiator capability. It is also desirable for the graft polymerization to be a living polymerization.
• the present invention concerns the provision of a substituted styrene polymer which may give a metallized polymer initiator having the above-described character­istics.
• the invention also concern the provision of a new graft copolymer having a plurality of side chains grafted to said substituted styrene polymer.
• a polymer consisting essentially of 0.1 to 100 mole% a recurring unit of the formula: wherein R1 is H or C1-C4 alkyl; and R2 is C2-C10 alkyl or alkoxy, unsubstituted or substituted phenyl, the substituent being C1-C4 alkyl, C1-C4 alkoxy or halogen (preferably in 4-position), or tri-(C1-C4 alkyl)silyl; and the balance of a recurring unit of the formula: wherein R1 is as defined and R3 is C1-C4 alkyl or alkoxy, or unsubstitued or substituted phenyl; a recurring unit of the formula: wherein R4 is H, C1-C4 alkyl or halogen; a position isomer of the unit of the formula (III); or a mixture of said units (II), (III) and its position isomerer; said polymer having
• a graft copolymer having a backbone polymer segment and a plurality of polymer side chains grafted thereto, wherein said backbone polymer is the afore­mentioned polymer having a plurality of vinylidene groups on the benzene ring, and wherein each of said polymer side chains is a polymer of an ethylenically unsaturated monomers capable of anion polymerization having a number average molecular weight from 500 to 1,000,000 per chain, said polymer side chains being grafted to said backbone polymer at said plurality of pendant vinylidene groups.
• the above graft copolymer may be produced by the steps of reacting the afore-mentioned polymer having a plurality of pendant vinylidene groups with a compound of the formula MR4, wherein M is a metal of group Ia in the periodic table and R5 is a hydrocarbon radical to metallize said pendant vinylidene groups, graft­polymerizing a monomcr capable of anion polymerization to each metallized site of said starting polymer until each grafted polymer chain has a number average molecular weight of 500 to 1,000,000.
• said graft coplymer may be produced by first preparing a living polymer having a number average molecular weight of 500 to 1,000,000 and then coupling the living terminal of said living polymer to said pendant vinylidene groups of the starting backbone polymer.
• terminals of said polymer side chains of the resulting graft copolymer may be chemically modified to have a plurality functional groups capable of crosslinking.
• the present invention has a number of important advantages over the prior art graft copolymers.
• the pendant vinylidene groups possessed by starting back­bone polymer may be metallized almost quantitatively. Since the polymer is metallized in the vicinity of a bulky substituent, the metallized polymer is less liable to association because of steric hinderance. It is for this reason that the metallized polymer is soluble in most of nonpolar organic solvents. The steric hinderance also serves to suppress undesirable side reactions such as carbonyl addition to the metal­lized site. All of the above features lead to a high yield of desired graft copolymer.
• the starting backbone polymer itself may be obtained in a high yield and its metallization may be performed almost quantitatively. This permits the backbone polymer and its metallized product to be purified very easily and thus simplifies the entire operation.
• Examples of monomers of the formula I-a include 1-phenyl-1-(4-vinylphenyl)ethylene, 1-(4-methylphenyl)-­1-(4-vinylphenyl)ethylene, 1-(4-propylphenyl)-1-(4-­vinylphenyl)ethylene, 1-trimethylsilyl-1-(4-vinyl­phenyl)ethylene and the like.
• Examples of monomers of the formula II-a include styrene, p-or m-methylstyrene, p-chlorostyrene, P-­methoxystyrene, ⁇ -methyl-styrene, isobutene and the like.
• the starting backbone polymer may be the homo­polymer of a monomer of the formula I-a. Up to 99.0 mole% thereof may be replaced by monomer II-a, III-a or a combination these monomers.
• the backbone polymer may be produced by anion- or cation polymerizing the above monomer or monomers by per se known methods.
• Examples of usable anion polymerization initiators include n-butyl lithium, sec-butyl lithium, ter-butyl lithium, naphthalene sodium, cumyl potassium, cumyl cesium and the like.
• the quantity of the initiator in this step is not critical.
• the anion polymerization may be carried out at a temperature of -100°C to +80°C, more preferably from -80°C to +50°C in the atmosphere of an inert gas or under high vacuum in an inert organic solvent.
• Examples of usable organic solvents include ethers such as diethyl ether, methyl ethyl ether or tetrahydro­furan; aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene; and aliphatic hydrocarbons such as pentane, hexane, heptane or cyclohexane.
• ethers such as diethyl ether, methyl ethyl ether or tetrahydro­furan
• aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene
• aliphatic hydrocarbons such as pentane, hexane, heptane or cyclohexane.
• Examples of usable cation polymerization initiators include protonic acids such as perchloric acid, acetyl perchloric acid, sulfuric acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid, co-catalyst-containing metal halide initiators such as aluminum chloride, boron trifluoride or tin tetrachloride; and co-catalyst-containing organometallic initiators such as triethylaluminum, diethylaluminum chloride or ethylaluminum dichloride.
• protonic acids such as perchloric acid, acetyl perchloric acid, sulfuric acid, p-toluenesulfonic acid or trifluoromethanesulfonic acid
• co-catalyst-containing metal halide initiators such as aluminum chloride, boron trifluoride or tin tetrachloride
• the cation polymerization may be carried out in the atmosphere of an innert gas or under high vacuum in an inert organic solvent.
• Examples of usable organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene or chlorobenzene; aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane; and halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride or trichloroethane. Combinations of two or more solvents may also be used.
• aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene or chlorobenzene
• aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane
• halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride or trichloroethane. Combinations of two
• the reaction temperature ranges between -100°C and +80°C, preferably between -80°C and 0°C. Since higher temperatures tend to promote the crosslinking reaction of pendant vinylidene groups, the lower the better within the above range.
• the reaction time may vary from 1 minute to 72 hours depending upon the reaction temperature. Too long reaction time tends to induce the crosslinking reaction of pendant vinylidene groups and is therefore undesirable.
• the quantity of initiator may range between 0.05 to 100 mmols per mole of the monomer. Too small quantities may result in a prolonged reaction time. Conversely, excessive use is not economical and requires undue steps for removing the catalyst after use.
• the resulting polymers having a plurality of pendant vinylidene groups on the benzene ring are soluble in most of conventional organic solvents. They may be used as the starting backbone polymer in the synthesis of the graft copolymer to be discussed hereinafter. Also, they may be modified by reacting the pendant vinylidene group with various reagents to obtain a variety of functional polymers.
• the above polymer preferably has a number average molecular weight of 1,000 to 1,000,000.
• the polymer is first metallized by reacting with an alkali metal organic compound of the formula MR4, wherein M and R4 are as defined hereinbefore.
• metallic compounds examples include n-butyl lithium, sec-butyl lithium, tert-butyl lithium, cumyl potassium, cumyl cesium and the like.
• the quantity of metallizing agent is not critical provided that it is not large excess relative to the number of pendant vinylidene groups.
• the alkali metal organic compound is used nearly on equimolar basis relative to the pendant vinylidene groups, it is preferable to use 0.5 to 20 moles, more preferably 2 to 10 moles per mole of the metallic compound of a tertiary amine such as triethylamine or N-methylpyrrolidine in conjuction with the alkali metal organic compound. This is effective to prevent the metallized polymer from gelling when it contains residual vinyl groups.
• the metallizing reaction may be carried out at a temperature of -80°C to +80°C, preferably -20°C to +30°C in the atmosphere of an inert gas or under high vacuum in an inert organic solvent.
• solvents include ethers such as dimethoxyethane, diethyl ether or tetrahydrofuran, and aromatic hydro­carbons such as benzene, toluene, xylene or ethyl­benzene.
• concentration of the polymer in these solvents is not critical but preferably ranges between 2 and 8 w/v %.
• the number of grafting sites per molecule may be selectively controlled by adjusting the quantity of the alkali metal organic compound.
• the resulting metallized polymer may be used as a polymeric anion polymerization initiator for graft-copolymerizing suitable monomers thereto.
• Examples of usable monomers are acrylic or metha­crylic monomers such as methyl acrylatc, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, phenyl acrylate, benzyl acrylate, acrylonitrile and corresponding esters and nitrile of methacrylic acid; styrene or its derivatives such as styrene, m- or p-methylstyrene or ⁇ -methylstyrene; and diene monomers such as butadiene, isoprene or 1,4-hexadiene.
• acrylic or metha­crylic monomers such as methyl acrylatc, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, phenyl acrylate, benzyl acrylate, acrylonitrile and corresponding esters and nitrile of methacrylic acid
• these monomers should not have such a functional group that reacts with the polymeric anion polymerization initiator to inhibit the polymerization reaction.
• an amount of an alkali metal alkoxide may be added to the reaction mixture to decrease its viscosity and also to prevent gellation.
• the monomer is an acrylic or methacrylic ester
• the addition of an alkali metal alkoxide serves to increase the proportion of isotactic polymer segments in the side chains.
• the quantity of the alkali metal alkoxide may be up to 20 times, preferably up to 10 times in mole per each metallized site of the backbone polymer.
• Examples of usable alkali metal alkoxides include lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropylbenzyloxide, sodium isopropylbenzyloxide, lithium stearyloxide, sodium stearyloxide, lithium benzyloxide, sodium methoxide, potassium propoxide sodium benzyloxide and the like. These alkali metal alkoxides are not capable of initiating the polymeri­zation of acrylic or methacrylic esters.
• the graft polymerization reaction may be carried out at a temperature of -100°C to +80°C in the atmos­phere of an inert gas or under high vacuum in the inert organic solvent as used in the metallizing reaction.
• acrylic monomers When acrylic monomers are used, lower temperatures within the above range are preferable for preventing undesirable side reactions such as cyclization.
• the growth of side chain polymers takes place as a living polymerization reaction.
• a number average molecular weight of 500 to 1,000,000 is obtained for each side chain, the living growth terminal of each side chain is deactivated.
• the molecular weight of the side chain may be preselected by varying moles of grafting monomers per each metallized site of the backbone polymer.
• Deactivation of the living growth terminals of side chains may be effected by adding a suitable protic solvent such as methanol.
• a suitable protic solvent such as methanol.
• the living growth terminals may be reacted with an appropriate exogeneous reagent to introduce a function group such as amino, hydroxy, carboxyl, halo, mercapto, sulfony, epoxy and the like.
• reagents used for introducing hydroxy function to the side chain terminal include aldehydes such as formaldehyde, acetaldehyde, n-butylaldehyde, chloral, propionaldehyde, isobutylaldehyde, n-valer­aldehyde, n-capraldehyde, n-heptaldehyde or stearyl­aldehyde; ketones such as acetone, methylethylketone or diethylketone; alkylene oxides and derivatives thereof such as ethylene oxide, propylene oxide, trimethylene oxide, butylene oxide, pentylene oxide, cyclohexylene oxide or styrene oxide. Oxygen gas may be used to introduce a hydroxy function.
• aldehydes such as formaldehyde, acetaldehyde, n-butylaldehyde, chloral, propionaldehyde, isobut
• Carbon dioxide may be reacted to introduce a caboxyl function.
• Imines such as ethyleneimine, propyleneimine or cyclohexeneimine may be used for introducing an amino function to the side chain terminals.
• Carbon disulfide, ethylenesulfide, propylene­sulfide and elementary sulfur may be used for introduc­ing a mercapto function.
• Sulfuryl chloride and epich­ lorhydrine may be used for introducing sulfonyl and epoxide function, respectively.
• the time required for the completion of the above reaction up to the introduction of functional groups to the side chain terminals may vary between one minutes and 72 hours depending upon the nature of particular reactants, reaction temperature and the like.
• the side chain polymer may be prepared separately in the form of a living polymer and then coupled to the pendant vinylidene groups present in the backbone polymer.
• the same alkal metal organic compound of the formula MR4 as used in the previous embodiment may be used as a polymerization initiator.
• Examples of usable monomers are acrylic or metha­crylic monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, phenyl acrylate, benzyl acrylate, acrylonitrile, and corresponding esters and nitrile of methacrylic acid; styrene or its derivatives such as styrene, m- or p-methylstyrene or ⁇ -methylstyrene; and diene monomers such as butadiene, isoprene or 1,4-hexadiene.
• acrylic or metha­crylic monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, phenyl acrylate, benzyl acrylate, acrylonitrile, and corresponding esters and nitrile of methacrylic acid
• an amount of an alkali metal alkoxide may be added to the reaction mixture to decrease its viscosity and also to prevent gellation.
• the addition of an alkali metal alkoxide serves to increase the proportion of isotactic polymer segments in the side chains.
• the quantity of the alkali metal alkoxide may be up to 20 times, preferably up to 10 times in mole per each mole of the initiator alkali metal compound.
• Examples of usable alkali metal alkoxides include lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropylbenzyloxide, sodium isopropylbenzyloxide, lithium stearyloxide, sodium stearyloxide, lithium benzyloxide, sodium methoxide, potassium propoxide sodium benzyloxide and the like.
• the living polymerization reaction may be carried out at a temperature of -80°C to 100°C in thc atmosphere of an inert gas or under high vacuum in an inert organic solvent as used in the previous embodiment.
• the molecular weight of the living polymer may be controlled by adjusting the molar ratio of the monomer to the initiator.
• the coupling reaction of the living polymer with the backbone polymer may be carried out at a temperature of -30 to +100°C, preferably from -30 to +70°C in the atmosphere of an inert gas or under high vacuum in an inert organic solvent as described above.
• the reaction time may vary from 1 to 72 hours depending upon other reaction conditions.
• the number of side chains coupled to the backbone polymer may be controlled by adjusting the density of pendant vinylidene groups in the backbone polymer and the molar ratio of the living polymer to the backbone polymer.
• the resulting copolymer thus prepared has a unique configuration in which a plurality of polymer side chains extend from the middle of the backbone polymer. It is for this reason that the graft copolymer of the present invention has a viscosity lower than that of a straight chain linear polymer having a corresponding molecular weight and, therefore, is useful as a vehicle resin for use in formulating high-solids coating compositions.
• the graft copolymer is also useful as an adhesive because of its large free volume. Since substantially no homopolymer is formed, the overall production steps may be greatly simplified.
• various parameters of polymeric products were determined as follows. Polymer molecular weights and molecular weight distribution were determined using a differential refractometer, UV spectrophotometer, GPC provided with laser small angle nephelometer, osmotic pressure osmometer, vapor pressure osmometer and ultracentrifugation. Polymer compositions were determined by 1H-NMR, 13C-NMR or by means of the above GPC. The metallized percent of the backbone polymer was determined by 1H-NMR after coupling trimethylchloro­silane to the activated sitc of the backbone polymer followed by isolating the coupled product in pure form.
• hydroxy and acid numbers of hydroxy or carboxy terminated graft copolymers were determined by IR spectrophotometry, titration with KOH, ASTM E222-66 method, Zerewitinoff ⁇ s method or 1H-NMR of silylated products.
• PVPE 1-phenyl-l-(4-vinylphenyl) ethylene
• the reaction mixture was extracted with ethyl ether and the extract was evaporated to dryness to obtain an alcohol corresponding to PVPE.
• PVPE was obtained by dehydrating this alcohol with potassium hydrogen sulfate followed by distillation in vacuo. Yield was 50% of theory.
• the product was identified by IR sectrum, 1H-NMR, 13C-NMR and gas chromatography.
• Example 2 To a 300 ml round flask equipped with a three way valve was placed an amount of an initiator in purified toluene under the atmosphere of nitrogen gas. Then an amount of PVPE in toluene was added. After a certain length of time, a small amount of methanol was added to stop the reaction. The resulting polymer was purified as in Example 2. Various data are shown in Table 2. In run No. 2-2, the monomer was gelled almost instant­aneously.
• the monomcric composition was determined by intrapolating the molar absorbance coefficient at 280 nm (PVPE homopolymer) on a standard curve for polymer blends of PVPE homopolymer and polystyrene at varying ratios.
• copolymer No. 5-2 of Example 6 was freeze-dried from benzene and then dissolved in toluene.
• Example 7 was repeated at various conditions shown in Table 6. The results are also shown in Table 6.
• a flask was charged with 16.4 ml of a solution of metallized polymer No. 5-5 of Example 15 in toluene (0.75 g of metallized polymer), 30 ml of fully dehydrated toluene and 30 ml of a toluene solution of lithium benzyloxide (1.2 equivalents relative to the metallized site). Then 6.0 ml of methyl methacrylate (MMA) was added and allowed to react at -78°C for 1 hour. Then 6.6 ml of ethylene oxide was reacted for 30 minutes. The reaction mixture was then poured into methanol whereupon 6.1 g (95% of theory) of a graft copolymer was obtained.
• MMA methyl methacrylate
• the number average molecular weights of this graft copolymer and of each its side chain polymer calculated from the charged amount of MMA and the concentration of metallized site were 1.1 x 105 and 6.7 x 103, respectively.
• the 1H-NMR analysis of the graft copolymer revealed that the tacticity of the side chain polymer (syndiotactic/heterotactic/isotactic) was 6.7/16.6/76.8.
• the number average molecular weight of the side chain polymer was estimated to be 6.2 x 103 based on the peak intensity ratio of benzene proton to concentration of metallized site of the starting polymer.
• a flask was charged with 12.6 ml of a solution of metallized polymer No. 5-5 of Example 15 in toluene (0.58 g of metallized polymer), 30 ml of fully dehydrated toluene and 77 ml of a toluene solution of lithium benzyloxide (5.5 equivalents relative to the metallized site). Then 6.75 ml of MMA was added and allowed to react at -78°C for 15 minutes. Then 3.8 ml of ethylene oxide was reacted for 1 hour. The reaction mixture was then poured into methanol whereupon 7.0 g (100% of theory) of a graft copolymer was obtained.
• the number average molecular weights of this graft copolymer and of each its side chain polymer calculated as in Example 16 were 9.7 x 103 and 1.5 x 105, respec­tively.
• the 1H-NMR analysis of the graft copolymer revealed that the tacticity of the side chain polymer (sydiotactic/heterotactic/isotactic) was 3.3/9.0/88.2.
• the number average molecular weight of the side chain polymer was estimated to be 9.5 x 103 by the same method as described in Example 16.

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